Preparation of synthetic zeolite molecular sieves

ABSTRACT

In the manufacture of synthetic zeolites, the formation of unwanted, contaminating zeolites is inhibited by the addition to the reactant mixture of a basic nitrogen-containing dye, and makes it possible to synthesize new zeolites AG5 and AG6 herein defined by their compositions and X-ray diffraction patterns.

The present invention relates to improvements in or relating to the manufacture of synthetic zeolite molecular sieves, and in particular to the use of basic dyes containing nitrogen, to inhibit the formation of specific unwanted zeolitic phases, and as a result promote the formation of desired zeolite phases.

Surprisingly we have found that certain basic dyes (and salts and esters thereof) adsorb very strongly on specific zeolites, or only on zeolites having related framework structures. If such a basic dye (or dyes) is employed, as recommended in this invention, this property can be used to suppress the formation of unwanted zeolite products during the manufacture of more desirable products. It is believed that the basic dye or dyes adsorb on nuclei of unwanted species and inhibit nucleation and subsequent crystal growth. The net result of this discovery is that it is now possible to manufacture desired zeolite products under more advantageous operating conditions, which could not be employed in the absence of said basic dyes. Also we have found that it is possible to inhibit the formation of known zeolitic products and to promote the formation of novel zeolites AG5 and AG6. Examples of some basic dyes suitable for this invention are shown in Table 1, but this table in no way limits the scope of our invention.

The present invention provides a process for the manufacture of synthetic zeolites, wherein the normal reaction of the reactant mixture is altered by the addition thereto of an additive comprising a basic dye or mixture of dyes containing, nitrogen (or salts or esters of such dyes), the additive: Al₂ 0₃ molar ratio being less than 0.1:1.

Such a basic dye containing nitrogen is one which promotes the formation of unwanted zeolite products. A suitable additive is a basic dye (or mixture of dyes) which adsorbs strongly on unwanted zeolite products.

                  TABLE 1                                                          ______________________________________                                         ADSORPTION ON ZEOLITES                                                                       STRONG       MEDIUM                                              ZEOLITE      ADSORPTION  STRONG ADSORPTION                                     ______________________________________                                         B (near gismondite)                                                                        crystal violet                                                                              methyl violet                                                     nuclear fast red                                                                            methylene blue                                        R (near chabazite                                                                          toluidene blue                                                     sodium)     methylene blue                                                     D (near chabazite                                                                          toluidene blue                                                     potassium-sodium)                                                                          methylene blue                                                     KM (potassium near                                                                         malachite green                                                                             magenta                                                 phillipsite)                                                                             nuclear fast red                                                                            crystal violet                                                                 methyl violet                                                                  methylene blue                                        F           methylene blue                                                                 malachite green                                                    A           acriflavine                                                        X, Y, Y.sup.1            acriflavine                                           ______________________________________                                    

In the manufacture of the faujasite-type zeolites commonly designated zeolites X, Y and Y¹, and of zeolite L, the prior art routes require, especially for commercial scale manufacture, that the reactants should be mixed and aged quiescently at ambient temperature, and then heated rapidly to a crystallization temperature of, for example, 100° C. Zeolite Y¹ is a higher silica modification of zeolite Y; both zeolites Y and Y¹ are treated as identical in the U.S. Pat. No. 3,130,007, while British Patent Specifications Nos. 909,266 and 972,831 distinguish between the Y and Y¹ form, respectively. This temperature is maintained for from 48 to 120 hours, and quiescent conditions are of vital importance, ie the reactants must undergo no significant mechanical agitation, and there must be no significant thermal gradients across the reaction mixture. Such conditions are, of course, extremely difficult to maintain in large scale commercial processes.

Alternatively, for the manufacture of zeolite X, Y and Y¹, the need for quiescent ageing and quiescent crystallization can be avoided by the use of active silicates, as in British Pat. No. 1,145,995, in which process ambient ageing stages are unnecessary and crystallization need not be quiescent. The limitations of the process of British Pat. No. 1,145,995 are that active silicates are essential, and that for synthetic faujasites having SiO₂ /Al₂ O₃ ratio >4 it is necessary to use expensive colloidal silica or fume silica as the major silica source in those manufacturing ranges which are economical in raw material usage. Where the SiO₂ /Al₂ O₃ ratio of the reaction mixture is ≦14, even with colloidal silica the reactions are unreliable and liable to give high levels of contamination with an undesirable small-port zeolite S.

In our co-pending British Patent application No. 4130/73, now British Patent Specification No. 1,450,411, (corresponding to U.S. application Ser. No: 435,507 filed 22 Jan. 1974, now abandoned) we have shown that it is possible to manufacture highly crystalline potassium or sodium/potassium faujasite under conditions which combine the advantage of easy manufacturing conditions with the use of cheaper raw materials, namely the replacement of colloidal or fume silica as the major source of silica by common water glass or other low-cost forms of silica, eg precipitated silica. A minor source of silica, necessary for the process of our said co-pending British Pat. Appln. 4130/73, is an active hydrated sodium metasilicate or active silica (as in British Pat. Nos. 1,145,995 and 1,193,254). For the purposes of our said co-pending British application No. 4130/73, an active silica(te) is defined as a source of silica, which must yield substantially pure synthetic faujasite within 17 hours at 85° in a vigorously agitated reaction, and wherein the reaction mixture molar ratios are: SiO₂ /Al₂ O₃ = 6.4, Na₂ O/SiO₂ = 0.35, H₂ O/Na₂ O = 50, SO₄ /Al₂ O₃ = 1.5. The sulphate is introduced as aluminium sulphate, and the remainder of the alumina as sodium aluminate. The ratio of active silica(te) to silica(te) from other sources is 1:3.6. While the process of our said co-pending British application No. 4130/73 yields zeolite Y or Y¹ of high purity, it has some limitations. It is essential that a minor part of the silica(te) should be in active form; also, as in the prior art processes, synthetic faujasites, when formed, may recrystallize to yield zeolite B if left in contact with the mother liquor for too long. Attempts to reduce reaction times by raising the temperature are ultimately limited by this conversion of Y or Y¹ to zeolite B, because before all of the reaction mixture has been crystallized as zeolite Y or Y¹, some of the product recrystallizes as zeolite B giving rise to high levels of contamination.

Similarly, in the process of our said co-pending British Patent application No. 4130/73, as in the prior art processes, attempts to reduce reaction time by seeding with pure zeolite Y or Y¹ would fail, because some of the added seed is converted to zeolite B, which in turn promotes formation of more zeolite B. Examples of the effects of this over-run problem are given in Table 2.

                                      TABLE 2                                      __________________________________________________________________________     MANUFACTURE OF ZEOLITE Y (SiO.sub.2 /Al.sub.2 O.sub.3 = 4.9)                            REACTION                                                                               CRYSTALLIZATION                                               METHOD USED                                                                             TIME HOURS                                                                             TEMPERATURE ° C                                                                     PRODUCT                                           __________________________________________________________________________     As in US 40*     95         95% zeolite Y                                      Patent                      + zeolite S                                        3,130,007                                                                               26*     103        70% zeolite Y                                                                  + amorphous                                                 27*     103        80% zeolite Y                                                                  + 20% zeolite B                                             12Δ                                                                              103        60% zeolite Y                                                                  30% zeolite B                                                                  10% amorphous                                      As in our                                                                               24-28   85         100% zeolite Y                                     said Co- 161/2   95         80% zeolite Y                                      pending                     + amorphous                                        British  17      95         100% zeolite Y                                     Applicaton                                                                              171/2   95         80% zeolite Y                                      No.: 4130/73                + 20% zeolite B                                    __________________________________________________________________________      *Also aged 28 hours at 25° C                                            Δ20% seed added, no preaging                                       

We have now found that if a suitable basic dye containing nitrogen is introduced into a zeolite reaction, preferably along with the siliceous components, then synthetic faujasites with SiO₂ /Al₂ O₃ = 2.3 to 6.3 can be prepared under highly advantageous conditions. Suitable dyes are, for example, crystal violet, methyl violet, and nuclear fast red. The advantages result (a) from the suppression of zeolite B formation, ie there are none of the over-run problems which occur in prior art routes; (b) from the fact that any hydrated sodium metasilicate can be employed as a minor source of silica, and its activity is of no significance; (c) the reaction time can be reduced substantially by either raising the temperature, or by adding zeolite seeds, or both. Typical results obtained by the process of this invention are given in Table 3, and are compared with results obtained by the process of this invention are given in Table 3, and are compared with results obtained in the absence of added organic components. The operating range for zeolite X manufacture in the temperature range 50° C to 120° C is as follows, on a molar basis:

wherein M₂ O = Na₂ O + K₂ O

SiO₂ /Al₂ O₃ = 2.7 to 8

M₂ o/siO₂ = 0.3 to 6.0

Na₂ O/M₂ O = 0.7 to 1.0

sodium metasilicate hydrate / Al₂ O₃ = 0.3 to 6.0

H₂ o/m₂ o = 10 to 150

basic dye, eg crystal violet / Al₂ O₃ = 5 × 10⁻ ⁴ to 0.1.

The operating ranges for zeolite Y and Y¹, at from 75° C to 120° C, are as follows:

    __________________________________________________________________________                                              Basic dye                             Range                                                                              SiO.sub.2 /Al.sub.2 O.sub.3                                                           M.sub.2 O/SiO.sub.2                                                                     Na.sub.2 O/M.sub.2 O                                                                  H.sub.2 O/M.sub.2 O                                                                   A.sub.2 /n/Al.sub.2 O.sub.3                                                           additive/Al.sub.2 O.sub.3             __________________________________________________________________________     1     4 to 6.9                                                                            0.25 to 0.4                                                                             0.7 to 1.0                                                                            40 to 120                                                                             0 to 3.0                                                                              5×10.sup.-.sup.4 to 0.1         2   6.9 to 7.9                                                                             0.25 to 0.335                                                                          "      "      "      "                                     3   7.9 to 10                                                                             0.25 to 0.34                                                                            "      "      "      "                                     4   10 to 12                                                                              0.25 to 0.40                                                                            "      "      "      "                                     5   12 to 14                                                                              0.25 to 0.45                                                                            "      "      "      "                                     6   14 to 16                                                                              0.25 to 0.50                                                                            "      "      "      "                                     7   16 to 40                                                                              0.25 to 1.0                                                                             "      "      "      "                                     __________________________________________________________________________

wherein M₂ O = Na₂ O + K₂ O, and A = an acid radical of valence n, for example sulphate, nitrate or chloride introduced as the aluminium salt or salts. Also the ratio of hydrated sodium metasilicate to silica from other sources is preferably at least 1:8.

                                      TABLE 3 SYNTHETIC FAUJASITES                 __________________________________________________________________________     REACTANT MOLAR RATIOS                                                                                                Ratio                                                                          inactive                                                                       hydrated                                                                       metasilicate                                                                          REACTION                          Ex.                       Basic dye                                                                             Basic dye                                                                           to other                                                                              Time Temp                         No SiO.sub.2 /Al.sub.2 O.sub.3                                                          M.sub.2 O/SiO.sub.2                                                                 An/2/Al.sub.2 O.sub.3 *                                                               H.sub.2 O/M.sub.2 O                                                                 additive/Al.sub.2 O.sub.3                                                             additive                                                                            silica hours                                                                               ° C                                                                        Product                   __________________________________________________________________________     1  3.85  1    1.2    47   0      None 0.125   3    95                                                                              zeolite B + zeolite                                                            C                                                                              + amorphous                2  3.85  1    1.2    47   5 × 10.sup.-.sup.3                                                              crystal                                                                             0.125   3    95                                                                              zeolite X                                                   violet                                        3  5     0.7  25     47   5 × 10.sup.-.sup.3                                                              methyl                                                                              0      24    95                                                                              zeolite X                                                   violet                                        4  20    1    0.4    40   0      none 0.6    24    95                                                                              zeolite S + zeolite                                                            B                                                                              +  amorphous               5  20    1    0.4    40   5 × 10.sup.-.sup.3                                                              nuclear                                                                             0.6    24    95                                                                              zeolite Y.sup.1                                             fast red                                      6  6.86  1.0  0.32   63   5 × 10.sup.-.sup.3                                                              crystal                                                                             0.25   24    85                                                                              zeolite Y/Y.sup.1                                           violet                                        7                         0      none 0.25   14   103                                                                              zeolite Y/Y.sup.1          8                         0      none 0.25   14.5 103                                                                              80% zeolite                                                                    Y/Y.sup.1                                                                      20% zeolite B              9                         5 × 10.sup.-.sup.3                                                              methyl                                                                              0.25   14 to                                                                               103                                                                              zeolite Y/Y.sup.1                                           violet      24                                10                        5 × 10.sup.-.sup.4                                                              methyl                                                                              0.25   14 to                                                                               103                                                                              zeolite Y/Y.sup.1             As in Example 6               violet      16                                11                        0      20%  0.25    7   103                                                                              50% zeolite Y                                               zeolite            30% zeolite B                                               Y seed             + amorphous                12                        5 ×  10.sup.-.sup.3                                                             crystal                                                                             0.25    7   103                                                                              zeolite Y/Y.sup.1                                           violet                                                                         and 20%                                                                        zeolite                                                                        Y seed                                        __________________________________________________________________________      *An acid radical of valence n, preferably SO.sub.4.sup.-.sup.-, but            possibly NC.sub.3.sup.-  or Cl.sup.--                                    

In the same manner, it is possible to manufacture zeolite L and the related zeolites, such as AG4 (disclosed in our co-pending British Patent Appln. No. 5492/72, now British Patent Specification No. 1,394,163 which corresponds to U.S. Application Serial No. 329,336 filed 5 May 1973, now abandoned) and a novel zeolite AG5 under advantageous conditions. Thus, in the prior art synthesis of zeolite L, there is always a tendency for the formation of unwanted zeolite KM, a small-port near-phillipsite; this can result from inadequate preageing of the reaction mixture at ambient temperature, or can result from agitation, either mechanical or resulting from thermal gradients, because quiescent crystallization is an essential feature of the manufacture and, especially on a commercial scale, true quiescent conditions are extremely difficult to maintain. Over-run problems occur in zeolite L synthesis, as with zeolites Y and Y¹, the unwanted conversion products being zeolite KM or, in some cases, zeolite D.

We have found that malachite green, magenta, crystal violet, methyl violet and nuclear fast red adsorb strongly on zeolite KM, and can be used to suppress the formation of this zeolite. A further advantage found is that with the basic dye added to the reaction mixture, amibent ageing stages are unnecessary and, futhermore, agitation is preferable, ie problems relating to disturbance from mixing and by thermal agitation became non-existent. Typical results are given in Table 4. Where a basic dye additive was incorporated, crystallization under agitated conditions yielded zeolites L or AG4 or AG5, instead of the expected zeolite KM. Non-agitated reactions yielded near-chabazites along with near L-type zeolites. A further advantage over the prior art synthesis is that cheap sources of silica, eg water glass, can be employed instead of expensive colloidal or fume silica.

Zeolite AG4 is a large-port L-type disclosed in our said co-pending British Patent Application No. 5492/72, and it can be readily distinguished from zeolite L by its ability to adsorb up to about 20% of perfluorotributylamine (PFTB) at P/po = 0.6 within 4 hours, whereas zeolite L adsorbs <1% under such conditions. This demonstrates that zeolite AG4 has ports of about 11.0A, as compared with zeolite L which has ports of about 9A. The novel zeolite AG5 is a small-port near L-type zeolite which as ports of about 6.5A, as indicated by its refusal of cumene (6.9A) and adsorption of 8% cyclohexane (6A) at P/po = 0.6 for 1 hour (under these conditions zeolite AG4 and zeolite L adsorb >8% cumene).

                                      TABLE 4                                      __________________________________________________________________________     ZEOLITES L, AG4 and AG5                                                        __________________________________________________________________________     REACTION RATIOS                           REACTION                                  Type of                        Basic dye                                  Example                                                                             silicate SiO.sub.2 /                                                                         *K.sub.2 O/                                                                         *M.sub.2 O/                                                                          *H.sub.2 O/                                                                          additive/                                                                            Time                                                                               Temp                             No   used     Al.sub.2 O.sub. 3                                                                   M.sub.2 O                                                                            SiO.sub.2                                                                           M.sub.2 O                                                                            Al.sub.2 O.sub. 3                                                                    hours                                                                              ° C                                                                          Product                     __________________________________________________________________________     13   Potassium                      5 × 10.sup.-.sup.3                        waterglass                     (crystal                                        SiO.sub.2 /K.sub.2 O=2.24                                                               14   1.0  0.55  100    violet)                                                                             48  95  zeolite AG5                  14   As Example 13                                                                           14   1.0  0.55  100   None  48  95  zeolite KM                   15   colloidal                      5 × 10.sup.-.sup.3                        silica   20   1.0  0.65  80    (crystal                                                                             72  95  zeolite AG5                                                       violet)                                   16   potassium                      5 × 10.sup.-.sup.3                        waterglass                     (methyl                                         SiO.sub.2 /K.sub.2 O=3.2                                                                20   0.64 0.425 37.5   violet)                                                                             48  95  zeolite AG4                  17   colloidal                                                                                7   0.64 0.8   70    5 × 10.sup.-.sup.3                                                             24  95  zeolite                                                                        AG4- silica     (nuclear                                                       5                                                                fast red)                                  18   potassium                                                                               28   0.58 0.452 32    5 × 10.sup.-.sup.3                                                             54  95  zeolite L                         waterglass                     crystal                                         SiO.sub.2 /K.sub. 2 O=3.2      violet                                     19   colloidal                                                                               20   0.3  0.3   40    5 × 10.sup.-.sup.3                                                             96  95  zeolite L                         silica                         (malachite                                                                      green)                                    __________________________________________________________________________      *M.sub.2 O = K.sub.2 O + Na.sub.2 O                                      

                  TABLE 5                                                          ______________________________________                                         X-ray diffractometer results                                                   ______________________________________                                         ZEOLITE     ZEOLITE                                                            AG5         AG4           ZEOLITE L                                                   100I/             100I/         100I/                                   dA     I.sub.o  dA       I.sub.o                                                                               dA     I.sub.o                                 ______________________________________                                         16.0   100      15.85    100    15.8   100                                     7.8    22                       7.89   8                                                       7.50      26    7.49   14                                      6.25   22                                                                      6.00   15.5     6.00      32    5.98   20                                      4.79   62                                                                      4.60   67       4.57      66    4.57   30                                                      4.40      26    4.40   7                                       4.15   78                                                                      3.87   37       3.91      77    3.91   35                                                                      3.78   10                                      3.66   37       3.66      32    3.66   18                                      3.42   70       3.46      55    3.48   25                                      3.25   53                       3.26   25                                      3.17   50                                                                      3.10   80       3.06      72    3.03   27                                                                      3.02   12                                                      2.91      58    2.91   25                                      2.80   61                                                                      2.68   14       2.65      47    2.65   16                                      2.60   11                       2.62   6                                       2.57    9                                                                                      2.49      11    2.45   11                                                                      2.42   21                                      2.32   27                                                                      2.17   30       2.19      13    2.19   9                                       ______________________________________                                    

X-ray diffraction data given in Table 5 illustrate that there are small but significant differences between zeolites L, AG4 and AG5.

The operating range for zeolite L, from 50° C to 120° C is for agitated reactions only, and is as follows:

SiO₂ /Al₂ O₃ = 20 to 28

M₂ o/siO₂ = 0.3 to 0.6

K₂ o/m₂ o = 0.26 to 1.0

H₂ o/m₂ o = 10 to 90

(basic dye)/Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1

wherein M₂ O = K₂ O + Na₂ O

The operating range for zeolite AG4, in agitated reaction only, at 50° C to 120° C is

SiO₂ /Al₂ O₃ = 7 to 20

M₂ o/siO₂ = 0.4 to 0.9

K₂ o/m₂ o = 0.5 to 0.95

H₂ o/m₂ o = 10 to 80

(basic dye)Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1

wherein M₂ O = K₂ O + Na₂ O

The operating range for novel zeolite AG5, in agitated reaction only, at 50° C to 120° C is

SiO₂ /Al₂ O₃ = 7 to 20

K₂ o/siO₂ = 0.45 to 0.65

H₂ o/k₂ o = 80 to 140

(basic dye)Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1

The invention therefore also provides a process for preparing the novel zeolite AG5 from a reactant composition according to the immediately preceding paragraph.

The novel zeolite AG5 has a composition in the following range, and its cations are exchangeable:

0.7 to 1.1 K₂ O.Al₂ O₃.2.5 to 6.0SiO₂.yH₂ O,

where y is 0 to 8.

The invention therefore also provides the novel zeolite AG5 having a composition according to the immediately preceding paragraph and an X-ray diffraction pattern substantially as shown in Table 5.

The experiments given below in Table 6 further illustrate the utility of this invention. In the field of synthesis normally yielding either zeolite F or zeolite D, the addition of both malachite green and methylene blue suppresses the formation of both zeolites, and allows formation of a novel zeolite AG6 (see Table 6). X-ray diffraction data is given in Table 7 for the novel zeolite AG6.

This novel zeolite AG6 has a composition in the following range, and its cations are exchangeable:

0.7 to 1.1 (x K₂ O. (1-x) Na₂ O) Al₂ O₃ .2.5 to 6.0 SiO₂.y H₂ O,

wherein x is 0.2 to 0.8, and y is 0 to 8.

The invention therefore further provides the novel zeolite AG6 having a composition according to the immediately preceding paragraph and an X-ray diffraction pattern substantially as shown in Table 7.

The operating range for the manufacture of zeolite AG6, in the temperature range 50° C to 120° C is as follows, ambient ageing being unnecessary, and agitation being optional:

SiO₂ /Al₂ O₃ = 1 to 10

K₂ o/na₂ O + K₂ O = 0.4 to 0.9

M₂ o/siO₂ = 0.4 to 4.0

H₂ o/m₂ o = 10 to 50

(basic dye(Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1

wherein M₂ O = K₂ O + Na₂ O

The invention therefore further provides a process for preparing the novel zeolite AG6 from a reactant composition according to the immediately preceding paragraph.

                                      TABLE 6                                      __________________________________________________________________________     REACTION MIXTURE MOLAR RATIOS             REACTION                             EXAMPLE                          basic dye                                                                               Time                                 NUMBER                                                                               SiO.sub.2 /Al.sub.2 O.sub.3                                                           K.sub.2 O/Na.sub.2 O+K.sub.2 O                                                         M.sub.2 O/SiO.sub.2                                                                  H.sub.2 O/M.sub.2 O                                                                  additive/Al.sub.2 O.sub.3                                                               hours                                                                              Product                          __________________________________________________________________________     20    5      0.8     2.8   13    0        24  zeolite F                        21    5      0.8     2.8   13    5 × 10.sup.-.sup.3.sup.+                                                          24  zeolite AG6                      22    5      0.4     2.5   20    5 × 10.sup.-.sup.3.sup.+                                                          36  zeolite AG6                      23    5      0.4     2.5   20    0        36  zeolite D                        __________________________________________________________________________      .sup.+equal (molar) quantities of malachite green and methylene blue     

                  TABLE 7                                                          ______________________________________                                         ZEOLITE 6 - X-RAY DIFFRACTION DATA                                             dA       9.36   7.05   6.24 5.42 3.116 2.978 2.618                             ______________________________________                                         100I/I.sub.o                                                                            100    20     35   25   30    70    20                                ______________________________________                                     

I claim:
 1. In a process for the manufacture of synthetic zeolites, comprising crystallizing the zeolite from a reaction mixture, the improvement comprising altering the reaction mixture by the addition thereto of an additive selected from the group consisting of crystal violet, methyl violet, nuclear fast red, methylene blue, toluidene blue, malachite green, magenta, acriflavine, and mixtures, salts and esters thereof.
 2. Process as claimed in claim 1, in which the silica source includes hydrated sodium metasilicate and the ratio of such silica source to other silica sources in the reactant mixture is at least 1:8.
 3. Process as claimed in claim 1, for producing zeolite L, which comprises reacting, under agitated conditions and at a temperature between 50° C and 120° C, a reactant mixture having a molar composition in the range:SiO₂ /Al₂ O₃ = 20 to 28 M₂ o/siO₂ = 0.3 to 0.6 K₂ o/m₂ o = 0.26 to 1.0 H₂ o/m₂ o = 10 to 90 (basic dye)/Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1wherein M₂ O = K₂ 0 + Na₂ O
 4. Process as claimed in claim 1, for producing zeolite AG4, which comprises reacting, under agitated conditions and at a temperature between 50° C and 120° C, a reactant mixture having a molar composition in the range:SiO₂ /Al₂ O₃ = 7 to 20 M₂ o/siO₂ = 0.4 to 0.9 K₂ o/m₂ o = 0.5 to 0.95 H₂ o/m₂ o = 10 to 80 (basic dye)/Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1wherein M₂ O = K₂ O + Na₂ O
 5. A method of crystallizing zeolite AG5 having the composition0.7 to 1.1 K₂ O . Al₂ O₃ . 2.5 to 6.0 SiO₂ . 0 to 8 H₂ Oand the following X ray diffraction pattern:

    ______________________________________                                         dA               100I/I.sub.o                                                  ______________________________________                                         16.0             100                                                           7.8              22                                                            6.25             22                                                            6.00             15.5                                                          4.79             62                                                            4.60             67                                                            4.15             78                                                            3.87             37                                                            3.66             37                                                            3.42             70                                                            3.25             53                                                            3.17             50                                                            3.10             80                                                            2.80             61                                                            2.68             14                                                            2.60             11                                                            2.57             9                                                             2.32             27                                                            2.17             30                                                            ______________________________________                                    

which comprises reacting together at 50°-120° C a silica source and an alumina source in a potassium-containing aqueous alkaline medium in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet and nuclear fast red, the molar ratio of the constituents of the mixture being represented by SiO₂ /Al₂ O₃ = 7 to 20 K₂ o/k.sub. 2 = 0.45 to 0.65 H₂ o/k.sub. 2 o = 80 to 140 (Basic dye)/Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1
 6. A method of crystallizing zeolite Y or Y¹ which comprises reacting together at 75°-120° C. a silica source and an alumina source in an aqueous alkaline medium containing sodium ions or sodium ions and potassium ions in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet, nuclear fast red, toluidine blue and methylene blue, the molar ratio of basic dye to alumina being in the range of 5 × 10⁻ ⁴ to 0.1 and the molar composition of the mixture including SiO₂ /Al₂ O₃ and M₂ O/SiO₂ which are selected in combination from

    ______________________________________                                         SiO.sub.2 /Al.sub.2 O.sub.3                                                                     M.sub.2 O/SiO.sub.2                                           ______________________________________                                          4 to 6.9        0.25 to 0.4;                                                  6.9 to 7.9       0.25 to 0.335;                                                7.9 to 10        0.25 to 0.34;                                                 10 to 12         0.25 to 0.40;                                                 12 to 14         0.25 to 0.45;                                                 14 to 16         0.25 to 0.50; or                                              15 to 40         0.25 to 1.0,                                                  ______________________________________                                    

and further including (b) Na₂ O/M.sub. 2 O = 0.7 to 1.0 H₂ o/m.sub. 2 o = 40 to 120 A_(2/n) /Al₂ O₃ = 0 to 3 to produce zeolite Y or Y¹, where M₂ O = Na₂ O + K₂ O and A is an acid radical of valence n.
 7. A method of crystallizing zeolite X which comprises reacting together at 50°-120° C a silica source and an alumina source in an aqueous alkaline medium containing sodium ions or sodium ions and potassium ions in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet, nuclear fast red, toluidine blue and methylene blue, the molar ratio of basic dye to alumina being in the range 5 × 10⁻ ⁴ to 0.1 and the molar composition of the mixture being represented bySiO₂ /Al.sub. 2 O₃ = 2.7 to 8 sodium metasilicate hydrate/Al.sub. 2 O₃ = 0.3 to 6.0 M₂ o/siO.sub. 2 = 0.3 to 6.0 Na₂ O/M.sub. 2 O = 0.7 to 1.0 N₂ o/m.sub. 2 o = 10 to 150 where M₂ O = Na₂ O + K₂ O to produce zeolite X.
 8. A method of crystallizing zeolite AG6 having the composition0.7 to 1.1 (xK₂ O.(1-x)Na₂ O₃ .2.5 to 6.0 SiO₂ to 8 H₂ O wherein x is 0.2 to 0.8, and the following X-ray diffraction pattern:

    ______________________________________                                         dA               100I/I.sub.o                                                  ______________________________________                                         9.36             100                                                           7.05             20                                                            6.24             35                                                            5.42             25                                                            3.116            30                                                            2.978            70                                                            2.618            20                                                            ______________________________________                                    

which comprises reacting together at 50°-120° C a silica source and an alumina in a potassium-containing aqueous alkaline medium in the presence of at least one basic dye selected from the group consisting of malachite green, magenta, crystal violet, methyl violet and nuclear fast red, the molar ratio of the constituents of the mixture being represented by SiO₂ /Al₂ O₃ = 1 to 10 K₂ o/na₂ O + K₂ O = 0.4 to 0.9 M₂ o/siO₂ = 0.4 to 4.0 H₂ o/m₂ o = 10 to 50 (basic dye)/Al.sub. 2 O₃ = 5 × 10⁻ ⁴ to 0.1 wherein M.sub. 2 O = K₂ O + Na₂ O, to produce zeolite AG6. 